US4623735A - Metal complex reaction product of furfurylamine and a metal carbonyl - Google Patents
Metal complex reaction product of furfurylamine and a metal carbonyl Download PDFInfo
- Publication number
- US4623735A US4623735A US06/755,800 US75580085A US4623735A US 4623735 A US4623735 A US 4623735A US 75580085 A US75580085 A US 75580085A US 4623735 A US4623735 A US 4623735A
- Authority
- US
- United States
- Prior art keywords
- carbonyl
- metal
- furfurylamine
- reaction product
- reimpregnation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 title claims description 5
- 150000004696 coordination complex Chemical class 0.000 title claims 5
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract description 30
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004634 thermosetting polymer Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/36—Furfuryl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
Definitions
- This invention relates to thermosetting, solventless polymers containing variable ratios of tungsten, molybdenum or chromium chemically bonded in the polymer chain which have high char yield and which are particularly useful for multi-cycle reimpregnation of a carbon/carbon composite.
- a reimpregnation resin is a thermosetting polymer introduced as a liquid into the characteristic voids of a carbon/carbon composite. The resin is subsequently cured and heat treated, thus increasing the density of the composite. Selected polymers can be used to impart specific desired characteristics to the composite depending upon the ultimate application. Viable reimpregnation resins must maintain a suitably low viscosity during the reimpregnation process and, in addition, exhibit a relatively high char yield. "Multi-cycle reimpregnation" is the term applied when the reimpregnation process is repeated a number of times.
- U.S. Pat. No. 4,185,043 to Robert C. Shaffer discloses thermoplastic and thermosetting polymers which incorporate tungsten and/or molybdenum metal atoms.
- the metal atoms are incorporated into the polymer by reacting a monomer or polymer containing at least one free carboxyl group with a reaction product of tungsten or molybdenum carbonyl and pyrrolidine to obtain a polymer. It is disclosed that the polymers are useful as reimpregnation resins.
- the reaction product of furfurylamine and tungsten carbonyl, molybdenum carbonyl or chromium carbonyl reacts directly with furfuryl alcohol to produce a suitable multi-cycle reimpregnation polymer.
- the resulting dark, viscous polymer may be utilized neat or it may be diluted with furfuryl alcohol, a reactive solvent, or it may diluted with an inert solvent such as dimethylformamide. Because of the relatively low viscosity at moderate temperatures, the polymers of this inventions may be used in a multi-cycle reimpregnation process without a solvent.
- precise variation in metal content may be achieved while retaining the metal in atomic form in the polymer molecule.
- the cured resin possesses low porosity and high char yield, characteristics which render it particularly useful for multi-cycle reimpregnation. Very little tungsten is lost during the sequence of operations resulting in the final char.
- a complex is first prepared by reacting furfurylamine with a metal carbonyl selected from the group consisting of tungsten carbonyl, molybdenum carbonyl and chromium carbonyl.
- a metal carbonyl selected from the group consisting of tungsten carbonyl, molybdenum carbonyl and chromium carbonyl.
- the reaction of sterically unhindered amines, although not furfurylamine, with metal carbonyls is well known in the art, [see G. W. A. Fowles et al, "The Reactions of Group VI Metal Carbonyls with Pyrrolidine, Piperazine and Morpholine", Inorganic Chemistry, Vol. 3, No. 2, pages 257-259 (1964); and C. S. Kraihanzel et al, Inorganic Chemistry, Vol. 2, No. 3, pages 533-540 (1963)].
- the complexes are prepared by reacting from 4 to 12 moles of furfurylamine per mole of metal carbonyl for
- the furfuryl alcohol is reacted with the furfurylamine-metal complex by combining the two materials and heating the reaction mixture preferably within the range of about 25° C. to 180° C. for about 5-10 hrs.
- the conditions required for completion of the reaction of the furfurylamine-metal complex with furfuryl alcohol vary, depending on the ratios of reactants as set forth in the following table:
- the amount of metal in the finished resin may be controlled by varying the ratio of furfurylamine-metal complex to furfuryl alcohol in the thermoplastic polymer, and by varying the amount of furfuryl alcohol used as the reactive diluent.
- the polymers of this invention have the property of being both thermoplastic and thermosetting, i.e., at temperatures of up to about 180° C. they are thermoplastic, i.e., they may be heated to obtain a low viscosity flowable material which, upon cooling, solidifies. At higher temperatures, i.e., above about 200° C., the materials are thermosetting, i.e., curable.
- a mixture of tungsten hexacarbonyl (88 g, 0.25 mole) and furfurylamine (92 ml, 1.00 mole) is heated at about 120° C. with stirring under argon for about 16 hours.
- 100 ml of a 50% ethanol/50% water solution is added to cause precipitation of the golden-yellow complex.
- the solid is isolated by vacuum filtration and washing with ethanol/water, followed by vacuum drying.
- the impure product is moderately air-sensitive; the pure dry product is considerably less so. However, storage excluding air is advisable. Recrystallization, if necessary, is by solution in warm, oxygen-free furfurylamine, followed by precipitation with water.
- the infrared spectrum of the product indicates that it is W(CO) 4 (furfurylamine) 2 .
- the product does not melt, but decomposes gradually above 60° C.
- Furfuryl alcohol (2.08 moles) is added to 0.42 mole of the reaction product of tungsten hexacarbonyl and furfurylamine. The mixture is gradually heated to 160° C. over five hours with stirring. It is then maintained between 160°-170° C. until the desired viscosity is achieved. The resulting dark brown thermoplastic material is viscous-to-solid at room temperature, depending on the duration of heating. It can be diluted while hot with a reactive polar solvent such as furfuryl alcohol or with an inert polar solvent such as dimethyl formamide.
- a reactive polar solvent such as furfuryl alcohol or with an inert polar solvent such as dimethyl formamide.
- the resulting polymer may be used "neat" as a multi-cycle reimpregnation resin for a carbon/carbon composite by impregnating it into the voids of the composite.
- the polymer is then cured by heating at 200° C. for 20 hours.
- This cured thermoset resin when subsequently carbonized at 800° C. for one hour, contains approximately 35% tungsten by weight.
- the char contains 80-90% of the tungsten present in the polymer precursor.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Products (AREA)
- Polyethers (AREA)
Abstract
Metal complexes are obtained by reacting furfurylamine with a metal carbonyl selected from the group consisting of tungsten carbonyl, molybdenum carbonyl and chromium carbonyl. Multi-cycle reimpregnation resins are obtained by reacting one of these metal complexes with furfuryl alcohol.
Description
This is a division of application Ser. No. 611,729 filed May 18, 1984, now U.S. Pat. No. 4,588,799, issued May 13, 1986.
This invention relates to thermosetting, solventless polymers containing variable ratios of tungsten, molybdenum or chromium chemically bonded in the polymer chain which have high char yield and which are particularly useful for multi-cycle reimpregnation of a carbon/carbon composite.
With the advent of aerospace products, carbon/carbon composites having high densities have come into widespread use. One or a combination of the following three methods for densification of carbon/carbon composites is commonly employed: (1) high temperature consolidation; (2) chemical vapor deposition; and (3) multi-cycle reimpregnation. For applications involving large parts or complex shapes, multi-cycle reimpregnation has been found to be the most effective method for imparting oxidation resistance and energy absorbing characteristics through the use of specifically formulated polymers.
A reimpregnation resin is a thermosetting polymer introduced as a liquid into the characteristic voids of a carbon/carbon composite. The resin is subsequently cured and heat treated, thus increasing the density of the composite. Selected polymers can be used to impart specific desired characteristics to the composite depending upon the ultimate application. Viable reimpregnation resins must maintain a suitably low viscosity during the reimpregnation process and, in addition, exhibit a relatively high char yield. "Multi-cycle reimpregnation" is the term applied when the reimpregnation process is repeated a number of times.
U.S. Pat. No. 4,185,043 to Robert C. Shaffer discloses thermoplastic and thermosetting polymers which incorporate tungsten and/or molybdenum metal atoms. The metal atoms are incorporated into the polymer by reacting a monomer or polymer containing at least one free carboxyl group with a reaction product of tungsten or molybdenum carbonyl and pyrrolidine to obtain a polymer. It is disclosed that the polymers are useful as reimpregnation resins.
It has now been discovered that the reaction product of furfurylamine and tungsten carbonyl, molybdenum carbonyl or chromium carbonyl reacts directly with furfuryl alcohol to produce a suitable multi-cycle reimpregnation polymer. The resulting dark, viscous polymer may be utilized neat or it may be diluted with furfuryl alcohol, a reactive solvent, or it may diluted with an inert solvent such as dimethylformamide. Because of the relatively low viscosity at moderate temperatures, the polymers of this inventions may be used in a multi-cycle reimpregnation process without a solvent. By appropriate choice of the amounts of reactants, precise variation in metal content may be achieved while retaining the metal in atomic form in the polymer molecule. The cured resin possesses low porosity and high char yield, characteristics which render it particularly useful for multi-cycle reimpregnation. Very little tungsten is lost during the sequence of operations resulting in the final char.
A complex is first prepared by reacting furfurylamine with a metal carbonyl selected from the group consisting of tungsten carbonyl, molybdenum carbonyl and chromium carbonyl. The reaction of sterically unhindered amines, although not furfurylamine, with metal carbonyls is well known in the art, [see G. W. A. Fowles et al, "The Reactions of Group VI Metal Carbonyls with Pyrrolidine, Piperazine and Morpholine", Inorganic Chemistry, Vol. 3, No. 2, pages 257-259 (1964); and C. S. Kraihanzel et al, Inorganic Chemistry, Vol. 2, No. 3, pages 533-540 (1963)]. Preferably the complexes are prepared by reacting from 4 to 12 moles of furfurylamine per mole of metal carbonyl for from 4 to 20 hours at a temperature of from 60° to 150° C.
The furfuryl alcohol is reacted with the furfurylamine-metal complex by combining the two materials and heating the reaction mixture preferably within the range of about 25° C. to 180° C. for about 5-10 hrs. The conditions required for completion of the reaction of the furfurylamine-metal complex with furfuryl alcohol vary, depending on the ratios of reactants as set forth in the following table:
______________________________________
Ratio of Moles
of Complex to Time
Furfuryl alcohol
Temp. Range (Approximate)
______________________________________
1:3 25° C. to 160° C.,
5.0 hours
then 160° C. to 170° C.
0.5 hour
1:5 25° C. to 160° C.,
3.0 hours
then 160° C. to 175° C.
1.5 hours
1:7 25° C. to 160° C.,
5.0 hours
then 160° C. to 172° C.
3.0 hours
1:9 25° C. to 160° C.,
5.0 hours
then 160° C. to 180° C.
5.0 hours
______________________________________
The amount of metal in the finished resin may be controlled by varying the ratio of furfurylamine-metal complex to furfuryl alcohol in the thermoplastic polymer, and by varying the amount of furfuryl alcohol used as the reactive diluent.
The polymers of this invention have the property of being both thermoplastic and thermosetting, i.e., at temperatures of up to about 180° C. they are thermoplastic, i.e., they may be heated to obtain a low viscosity flowable material which, upon cooling, solidifies. At higher temperatures, i.e., above about 200° C., the materials are thermosetting, i.e., curable.
The following example illustrates the best mode contemplated for carrying out this invention.
A mixture of tungsten hexacarbonyl (88 g, 0.25 mole) and furfurylamine (92 ml, 1.00 mole) is heated at about 120° C. with stirring under argon for about 16 hours. To the cooled red-brown reaction mixture, 100 ml of a 50% ethanol/50% water solution is added to cause precipitation of the golden-yellow complex. The solid is isolated by vacuum filtration and washing with ethanol/water, followed by vacuum drying. The impure product is moderately air-sensitive; the pure dry product is considerably less so. However, storage excluding air is advisable. Recrystallization, if necessary, is by solution in warm, oxygen-free furfurylamine, followed by precipitation with water. The infrared spectrum of the product indicates that it is W(CO)4 (furfurylamine)2. The product does not melt, but decomposes gradually above 60° C.
Furfuryl alcohol (2.08 moles) is added to 0.42 mole of the reaction product of tungsten hexacarbonyl and furfurylamine. The mixture is gradually heated to 160° C. over five hours with stirring. It is then maintained between 160°-170° C. until the desired viscosity is achieved. The resulting dark brown thermoplastic material is viscous-to-solid at room temperature, depending on the duration of heating. It can be diluted while hot with a reactive polar solvent such as furfuryl alcohol or with an inert polar solvent such as dimethyl formamide. For maximum metal loading, the resulting polymer may be used "neat" as a multi-cycle reimpregnation resin for a carbon/carbon composite by impregnating it into the voids of the composite. The polymer is then cured by heating at 200° C. for 20 hours. This cured thermoset resin, when subsequently carbonized at 800° C. for one hour, contains approximately 35% tungsten by weight. The char contains 80-90% of the tungsten present in the polymer precursor.
Claims (4)
1. A metal complex comprising the reaction product of furfurylamine and a metal carbonyl selected from the group consisting of tungsten carbonyl, molybdenum carbonyl and chromium carbonyl.
2. A metal complex as defined in claim 1 wherein said metal carbonyl is tungsten carbonyl.
3. A metal complex as defined in claim 1 wherein said metal carbonyl is molybdenum carbonyl.
4. A metal complex as defined in claim 1 wherein said metal carbonyl is chromium carbonyl.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/755,800 US4623735A (en) | 1984-05-18 | 1985-07-17 | Metal complex reaction product of furfurylamine and a metal carbonyl |
| US06/927,967 US4833030A (en) | 1984-05-18 | 1986-11-07 | Polymer impregnated and carbonized carbon/carbon composite |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/611,729 US4588799A (en) | 1984-05-18 | 1984-05-18 | Reimpregnation resin comprising reaction product of metal complex and furfuryl alcohol |
| US06/755,800 US4623735A (en) | 1984-05-18 | 1985-07-17 | Metal complex reaction product of furfurylamine and a metal carbonyl |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/611,729 Division US4588799A (en) | 1984-05-18 | 1984-05-18 | Reimpregnation resin comprising reaction product of metal complex and furfuryl alcohol |
| US06611729 Division | 1985-05-18 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/927,967 Division US4833030A (en) | 1984-05-18 | 1986-11-07 | Polymer impregnated and carbonized carbon/carbon composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4623735A true US4623735A (en) | 1986-11-18 |
Family
ID=27086581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/755,800 Expired - Fee Related US4623735A (en) | 1984-05-18 | 1985-07-17 | Metal complex reaction product of furfurylamine and a metal carbonyl |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4623735A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4833030A (en) * | 1984-05-18 | 1989-05-23 | Hitco | Polymer impregnated and carbonized carbon/carbon composite |
| US20050203200A1 (en) * | 2002-04-19 | 2005-09-15 | Kutal Charles R. | Anionic and Lewis base photopolymerization process and its use for making optical articles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185043A (en) | 1976-08-16 | 1980-01-22 | Hitco | Polymers containing chemically bonded metal atoms |
-
1985
- 1985-07-17 US US06/755,800 patent/US4623735A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185043A (en) | 1976-08-16 | 1980-01-22 | Hitco | Polymers containing chemically bonded metal atoms |
Non-Patent Citations (3)
| Title |
|---|
| C. S. Kraihanzel et al, Inorganic Chemistry, vol. 2(3), Jun., 1963, pp. 533-540. |
| G. W. A. Fowles et al, Inorganic Chemistry, vol. 3, No. 2, Feb. 1964, pp. 257-259. |
| J. A. Connor et al, Jour. Organometallic Chemistry, vol. 24 (1970), pp. C20-C22. |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4833030A (en) * | 1984-05-18 | 1989-05-23 | Hitco | Polymer impregnated and carbonized carbon/carbon composite |
| US20050203200A1 (en) * | 2002-04-19 | 2005-09-15 | Kutal Charles R. | Anionic and Lewis base photopolymerization process and its use for making optical articles |
| US7253213B2 (en) * | 2002-04-19 | 2007-08-07 | Kutal Charles R | Anionic and Lewis base photopolymerization process and its use for making optical articles |
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